KR102554523B1 - Interlayer for tinted laminated glass and tinted laminated glass - Google Patents

Abstract

In the present invention, when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996), the visible light transmittance (Tv) is 5% or less, and the variation in visible light transmittance according to parts is small, and the aesthetic appearance It is an object to provide this excellent interlayer film for colored laminated glass and colored laminated glass using the interlayer film for colored laminated glass.
The present invention relates to an interlayer film for colored laminated glass having a concave portion on at least one surface and having a visible light transmittance (Tv) of 5% or less when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996). It is composed of a laminate of at least two layers of a first resin layer containing a thermoplastic resin and a colorant, and a second resin layer containing a thermoplastic resin and no colorant, the elastic modulus of the first resin layer (E ₁ ) and the elastic modulus (E ₂ ) of the second resin layer (E ₁ /E ₂ ) is 1.25 or more, and the thickness (t ₁ ) of the first resin layer and the thickness of the second resin layer An interlayer film for colored laminated glass having a (t ₂ ) ratio (t ₁ /t ₂ ) of 2.0 or less.

Description

Interlayer for tinted laminated glass and tinted laminated glass

The present invention is a colored plywood having a visible light transmittance (Tv) of 5% or less and excellent aesthetics with little variation in visible light transmittance when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996). It relates to an interlayer film for glass and colored laminated glass using the interlayer film for colored laminated glass.

Even if laminated glass is damaged by an external impact, it is safe with little scattering of glass fragments, so it is widely used as windshield, side glass, rear glass, roof glass of vehicles such as automobiles, and window glass of aircraft and buildings. It is being used. As laminated glass, laminated glass etc. which were integrated by interposing the interlayer film for laminated glass containing a liquid plasticizer and polyvinyl acetal resin between at least one pair of glass, for example are mentioned.

In recent years, the performance required for glass has also diversified, and colored laminated glass has been demanded from the viewpoints of design, privacy protection, light shielding, and the like. In particular, highly colored laminated glass having a visible light transmittance (Tv) of 5% or less can exhibit particularly high privacy protection, and is therefore preferably used for roof glass of vehicles and window glass of buildings and the like. In addition, as mirrorless automobiles equipped with in-vehicle cameras become popular, it is thought that highly colored laminated glass will also be used for side windows of automobiles.

Colored laminated glass is generally manufactured using an interlayer film for laminated glass blended with a colorant such as a pigment (for example, Patent Document 1). However, in order to achieve a visible light transmittance (Tv) of 5% or less by this method, it is necessary to blend a large amount of colorant into the interlayer for laminated glass. Interlayers for laminated glass containing such a large amount of colorant have a problem in that the visible light transmittance varies greatly depending on the part, and aesthetic problems occur.

Japanese Unexamined Patent Publication No. 2010-248026

In view of the above situation, the present invention, when laminated glass is manufactured using two sheets of clear glass conforming to JIS R3202 (1996), has a visible light transmittance (Tv) of 5% or less, and a visible light transmittance depending on the site. It is an object of the present invention to provide an interlayer film for colored laminated glass having a small variation in the aesthetic appearance, and a colored laminated glass using the interlayer film for colored laminated glass.

The present invention relates to an interlayer film for colored laminated glass having a concave portion on at least one surface and having a visible light transmittance (Tv) of 5% or less when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996). It is composed of a laminate of at least two layers of a first resin layer containing a thermoplastic resin and a colorant, and a second resin layer containing a thermoplastic resin and no colorant, the elastic modulus of the first resin layer (E ₁ ) and the elastic modulus (E ₂ ) of the second resin layer (E ₁ /E ₂ ) is 1.25 or more, and the thickness (t ₁ ) of the first resin layer and the thickness of the second resin layer An interlayer film for colored laminated glass having a (t ₂ ) ratio (t ₁ /t ₂ ) of 2.0 or less.

The present invention is described in detail below.

The inventors of the present invention have a concave portion on at least one surface, and an interlayer film for colored laminated glass having a visible light transmittance (Tv) of 5% or less when laminated glass is manufactured using two sheets of clear glass conforming to JIS R3202 (1996) In this study, the cause of the deviation of visible light transmittance according to the part was examined. As a result, it was found that the concave portion formed on the surface of the interlayer film for laminated glass was the cause. In the production of laminated glass, usually, a laminate in which an interlayer film for laminated glass is laminated between at least two glass plates is squeezed through a nip roll (squeeze degassing method), or placed in a rubber bag and vacuum degassed (vacuum degassing method). ), compressing while degassing the remaining air between the glass plate and the interlayer. Subsequently, laminated glass is manufactured by pressurizing and compressing the laminate by heating in an autoclave, for example. In the manufacturing process of laminated glass, degassing at the time of laminating glass and an interlayer film for laminated glass is important. Fine irregularities are formed on at least one surface of the interlayer film for laminated glass for the purpose of securing degassing properties during manufacture of laminated glass. In particular, the concave portion in the unevenness has a groove shape in which the bottom portion is continuous (hereinafter also referred to as "angular line shape"), and the concave portions on the adjacent angle line are regular and parallel. By setting it as the structure formed, very excellent degassing property can be exhibited. Since the concave portion formed on the surface of the interlayer film for laminated glass is usually filled during compression in the laminated glass manufacturing process, there was hardly any problem in the obtained laminated glass.

However, in the case of an interlayer film for laminated glass in which two or more resin layers including a colorant-containing layer are laminated, the present inventors, in the laminated glass obtained through the laminated glass manufacturing process, the influence of the recesses on the colorant-containing layer This remained, and it was found that variations in visible light transmittance occurred depending on the site.

That is, when a concave portion is formed on the surface of an interlayer film for laminated glass in which two or more resin layers including a layer containing a colorant are laminated using an embossing roll or the like, the concave portion is not only formed on the surface of the interlayer film, but also processed. It is thought that the pressure of the time transfers the concave portion to the interface between the layers of the resin layer, and the interface becomes uneven. In particular, it is considered that when the angled-line concave portion is formed on the surface, the angled-line concave portion is strongly transferred to the interface between layers. Although the depressions on the surface of the interlayer film are filled during compression in the laminated glass manufacturing process, the unevenness transferred to the interface between the layers of the resin layer remains. Such unevenness remaining at the interface of the resin layer is hardly recognized by the naked eye in a transparent portion, but is considered to be recognized as a deviation of visible light.

In contrast, the present inventors have determined that an interlayer film for colored laminated glass is composed of a laminate of at least two layers: a first resin layer containing a thermoplastic resin and a colorant; and a second resin layer containing a thermoplastic resin and no colorant. did Furthermore, by increasing the modulus of elasticity of the first resin layer, the transfer of concave portions to the interface was suppressed, and as a result, it was found that variation in visible light transmittance could be prevented, and the present invention was completed.

The interlayer film for colored laminated glass of the present invention is composed of a laminate of at least two layers: a first resin layer containing a thermoplastic resin and a coloring agent, and a second resin layer containing a thermoplastic resin and no coloring agent. The first resin layer has a role of adjusting the visible light transmittance of the interlayer film for colored laminated glass of the present invention.

The interlayer film for colored laminated glass of the present invention is preferably a laminate of three or more layers in which the first resin layer is sandwiched between two second resin layers. By setting it as such a laminated body of three or more layers, variation in visible light transmittance can be prevented even in the case of having concave portions on both surfaces.

The interlayer film for colored laminated glass of the present invention has a concave portion on at least one surface. In the interlayer film for colored laminated glass of the present invention, it is preferable that the concave portion has a groove shape (angular line shape) with a continuous bottom and is regularly arranged in parallel.

Further, in the interlayer film for colored laminated glass of the present invention, it is preferable that the concave portion has a groove shape with a continuous bottom and is parallel to each other. Furthermore, in the interlayer film for colored laminated glass of the present invention, it is preferable that the concave portions have a groove shape with a continuous bottom, and that the concave portions are arranged regularly in parallel.

In general, the ability of air to escape during pre-compression and final compression of a laminate in which an interlayer film for laminated glass is laminated between two glass plates is closely related to the communication and smoothness of the bottom of the concave portion.

By setting the shape of the concave portion of at least one surface of the interlayer film for laminated glass to a shape in which concave portions in the form of grooves with continuous bottoms are regularly paralleled, the bottom portion has better communication and significantly debonds during pre-compression bonding and final compression bonding. stamina is improved

In addition, by making the concave portion of at least one surface of the interlayer film for laminated glass a shape in which concave portions in the form of grooves with continuous bottoms are parallel to each other, the bottom portion is more excellent in communication and is remarkably superior at the time of pre-compression bonding and final compression bonding. Thus, the degassing property is improved.

In addition, by making the concave portion of at least one surface of the interlayer film for laminated glass a shape in which concave portions in the form of grooves with continuous bottoms are arranged in parallel and regularly, the bottom portion is further excellent in communication, and pre-compression bonding and bonding At the time of compression, the degassing property is further remarkably improved.

Further, "regularly paralleled" means that when the surface of the interlayer film having the concave portions is observed, the concave portions having the shape of grooves with continuous bottoms periodically in a certain direction are arranged in parallel. In addition, "parallelly paralleled" means that the adjacent recesses may be parallel at equal intervals, or even if the adjacent recesses are parallel and parallel, but the intervals of all adjacent recesses are not equal intervals. means to become

1 and 2 show schematic diagrams showing an example of an interlayer film for laminated glass in which groove-shaped concave portions having continuous bottoms are arranged at regular intervals and parallel to each other on the surface. 3, the surface of an interlayer film for laminated glass in which concave portions in the shape of grooves with continuous bottoms are regularly parallel to the surface was measured by a three-dimensional roughness measuring instrument (manufactured by KEYENCE, “KS-1100”, tip head model “LT-9510VM”). ) shows the image data of the three-dimensional roughness measured using .

A preferable lower limit of the roughness (Rz) of the surface having the concave portion is 5 μm, and a preferable upper limit is 90 μm. When the roughness (Rz) of the surface having the concave portion is within this range, excellent degassing performance can be exhibited.

In addition, in this specification, the roughness (Rz) of the surface which has the said concave part is measured by the method according to JIS B-0601 (1994).

In this specification, the roughness (Rz) of the surface having the concave portion is defined in JIS B-0601 (1994) "Surface Roughness-Definition and Display", by a method conforming to JIS B-0601 (1994), It means the 10-point average roughness (Rz) of the obtained interlayer. For the roughness (Rz) of the concave portion, for example, "Surfcorder SE300" manufactured by Kosaka Laboratories is used as a measuring instrument, and the stylus system conditions at the time of measurement are: cut-off value = 2.5 mm, reference length = 2.5 mm, evaluation length = It can be measured by measuring under conditions of 12.5 mm, tip radius of the stylus = 2 µm, tip angle = 60 °, and measurement speed = 0.5 mm/s. At this time, the environment at the time of measurement is set to 23 degreeC and 30 RH%. The direction in which the stylus is moved is perpendicular to the groove direction when the concave portion is in the shape of an angle line, and in an arbitrary direction when the concave portion is not in the shape of an angle line.

A preferable lower limit of the roughness (Rz) of the concave portion on each line is 10 μm, and a preferable upper limit is 90 μm. When the roughness (Rz) of the concave portion on each line is within this range, excellent degassing performance can be exhibited. A more preferable lower limit of the roughness (Rz) of the concave portion on each line is 20 μm, and a more preferable upper limit is 80 μm.

In addition, in this specification, the roughness (Rz) of the concave part on each line is measured by the method according to JIS B-0601 (1994) mentioned above.

A preferable lower limit of the distance between concave portions on the angular lines adjacent to each other is 10 μm, and a preferable upper limit is 500 μm. When the distance between the concave portions on each line is within this range, excellent degassing performance can be exhibited. A more preferable lower limit of the distance between the concave portions on each line is 50 μm, and a more preferable upper limit is 300 μm.

In addition, in the present specification, the spacing of the concave portions on each line is determined by using an optical microscope (for example, "BS-8000III" manufactured by SONIC, etc.) to determine the first surface and the second surface of the interlayer film for laminated glass (observation 20 mm x 20 mm) is observed, and the distance between adjacent concave portions is measured, and then the average value of the shortest distance between the lowermost portions of adjacent concave portions is calculated.

In the case where the concave portion is not in the shape of an angular line, the interval (Sm) of the concave portion of the surface having the concave portion is preferably 600 μm or less, more preferably 450 μm or less, still more preferably 400 μm or less, and particularly 350 μm or less desirable. This reduces the self-adhering force between the interlayer films for laminated glass when the interlayer film for laminated glass is wound up in a roll shape, thereby facilitating unwinding.

In addition, in this specification, the interval (Sm) of the concave portion when the concave portion is not in the shape of each line is, for example, JIS B-0601 (1994) "Surface Roughness - Definition and Display", JIS B-0601 ( 1994) means the average spacing (Sm) of concave portions on the surface of the interlayer film obtained by the method. The spacing (Sm) of the concave portion was measured by using "Surfcorder SE300" manufactured by Kosaka Laboratory Co., Ltd. as a measuring instrument, and the stylus system conditions at the time of measurement were: cut-off value = 2.5 mm, standard length = 2.5 mm, evaluation length = 12.5 mm, stylus It can measure by measuring under the conditions of tip radius = 2 micrometers, tip angle = 60 degrees, and measurement speed = 0.5 mm/s. At this time, the environment at the time of measurement is set to 23 degreeC and 30 RH%. The direction in which the stylus moves is set to an arbitrary direction.

Further, the first resin layer may be disposed on the entire surface of the interlayer film for colored laminated glass of the present invention, or may be disposed on only a part thereof. For example, a shade in a windshield of an automobile can be obtained by arranging the first resin layer only on a part of an interlayer film for laminated glass.

By using the interlayer film for colored laminated glass of the present invention as the laminate, the effect of suppressing transfer of the colorant from the resulting interlayer film for colored laminated glass can also be obtained.

An interlayer film for laminated glass is usually stored in a roll-shaped state, taken out from the roll-like body, and used for manufacture of laminated glass. In an interlayer film for laminated glass in which a large amount of colorant is blended so that the visible light transmittance (Tv) is 5% or less, a part of the colorant easily bleeds out on the surface of the interlayer film for laminated glass. In such an interlayer film for colored laminated glass, the bleed-out colorant may be transferred to another interlayer film for laminated glass or to the operator's hand during storage in the roll-shaped body or during work after being taken out of the roll-shaped body. By laminating the second resin layer containing no colorant, transfer of the colorant from the first resin layer containing the colorant can be prevented.

The said 1st resin layer contains a thermoplastic resin and a coloring agent.

As the thermoplastic resin, for example, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoroethylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyether , polyamide, polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal, ethylene-vinyl acetate copolymer and the like. Especially, it is preferable that the said resin layer contains polyvinyl acetal or an ethylene-vinyl acetate copolymer, and it is more preferable that it contains polyvinyl acetal.

The polyvinyl acetal can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The said polyvinyl alcohol can be manufactured by saponifying polyvinyl acetate, for example. The saponification degree of the said polyvinyl alcohol is generally in the range of 70-99.8 mol%.

The average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, even more preferably 1700 or more, particularly preferably more than 1700, preferably 5000 or less, more preferably 4000 or less. , more preferably 3000 or less, particularly preferably less than 3000. When the average degree of polymerization is equal to or greater than the lower limit, the penetration resistance of the laminated glass is further increased. When the average degree of polymerization is equal to or less than the above upper limit, molding of the interlayer film becomes easy.

The average degree of polymerization of the polyvinyl alcohol is obtained by a method based on JIS K6726 "Polyvinyl Alcohol Test Method".

The carbon number of the acetal group contained in the polyvinyl acetal is not particularly limited. The aldehyde used when producing the said polyvinyl acetal is not specifically limited. The preferable lower limit of the number of carbon atoms of the acetal group in the polyvinyl acetal is 3, and the preferable upper limit is 6. When the number of carbon atoms of the acetal group in the polyvinyl acetal is 3 or more, the glass transition temperature of the interlayer film is sufficiently lowered, and bleed-out of the plasticizer can be prevented. By setting the carbon number of aldehyde to 6 or less, synthesis of polyvinyl acetal is facilitated and productivity can be secured. The aldehyde having 3 to 6 carbon atoms may be a linear aldehyde or a branched aldehyde, and examples thereof include n-butylaldehyde and n-valeraldehyde.

The aldehyde is not particularly limited. As the aldehyde, generally, an aldehyde having 1 to 10 carbon atoms is preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butylaldehyde, isobutylaldehyde, n-valeraldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, n-octylaldehyde, n- nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, and benzaldehyde; and the like. Among them, propionaldehyde, n-butylaldehyde, isobutylaldehyde, n-hexylaldehyde or n-valeraldehyde is preferred, propionaldehyde, n-butylaldehyde or isobutylaldehyde is more preferred, and n-butylaldehyde is still more preferred. desirable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

The hydroxyl group content (hydroxyl group content) of the polyvinyl acetal is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 18 mol% or more, preferably 40 mol% or less, more preferably It is 35 mol% or less. When the content of the hydroxyl group is equal to or greater than the lower limit, the adhesive force of the interlayer film is further increased. In addition, when the hydroxyl group content is equal to or less than the above upper limit, the flexibility of the interlayer film increases and the handling of the interlayer film becomes easy.

The hydroxyl group content of the polyvinyl acetal is a value obtained by dividing the amount of ethylene groups to which the hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the hydroxyl group is bonded can be obtained by measuring, for example, based on JIS K6726 "Polyvinyl Alcohol Test Method" or ASTM D1396-92.

The degree of acetylation (acetyl group amount) of the polyvinyl acetal is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, even more preferably 0.5 mol% or more, preferably 30 mol% or less, more preferably is 25 mol% or less, more preferably 20 mol% or less. When the degree of acetylation is equal to or greater than the lower limit, the compatibility between polyvinyl acetal and the plasticizer increases. When the degree of acetylation is equal to or less than the above upper limit, the moisture resistance of the interlayer film and the laminated glass increases.

The degree of acetylation is a value expressed as a percentage of the mole fraction obtained by dividing the total amount of ethylene groups in the main chain by subtracting the amount of ethylene groups to which the acetal group is bound and the amount of ethylene groups to which the hydroxyl group is bound, from the total amount of ethylene groups in the main chain. . The amount of ethylene groups to which the acetal group is bonded can be measured in accordance with, for example, JIS K6728 "Testing methods for polyvinyl butyral" or ASTM D1396-92.

The acetalization degree (butyralization degree in the case of polyvinyl butyral resin) of the polyvinyl acetal is preferably 50 mol% or more, more preferably 53 mol% or more, still more preferably 60 mol% or more, particularly preferably Preferably it is 63 mol% or more, preferably 85 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less. When the degree of acetalization is equal to or greater than the lower limit, the compatibility between polyvinyl acetal and the plasticizer increases. When the degree of acetalization is equal to or less than the above upper limit, the reaction time required for producing polyvinyl acetal is shortened.

The degree of acetalization is a value expressed as a percentage of the mole fraction obtained by dividing the amount of ethylene groups to which the acetal group is bonded by the total amount of ethylene groups in the main chain.

The degree of acetalization is determined by measuring the degree of acetylation and the content of hydroxyl groups by a method based on JIS K6728 "Testing methods for polyvinyl butyral" or a method based on ASTM D1396-92, and calculating the mole fraction from the obtained measurement results, Then, it can be calculated by subtracting the degree of acetylation and the content of hydroxyl groups from 100 mol%.

The hydroxyl group content (hydroxyl group content), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from the results measured by a method based on JIS K6728 "Polyvinyl butyral test method". When the polyvinyl acetal is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl group amount), acetalization degree (butyralization degree) and acetylation degree are determined by a method based on JIS K6728 "Polyvinyl butyral test method" It is preferable to calculate from the measured results.

The colorant is not particularly limited, and pigments and dyes conventionally formulated in interlayers for laminated glass can be used. Among them, pigments are preferable because the visible light transmittance (Tv) of the interlayer film for colored laminated glass can be easily reduced to 5% or less.

The pigment is not particularly limited, and examples thereof include phthalocyanine, phthalocyanine derivatives, anthraquinone, anthraquinone derivatives, perylene, perylene derivatives, titanium oxide, titanium oxide derivatives, azo compounds, carbon black, and the like. can be heard Among them, phthalocyanine, a derivative of phthalocyanine, anthraquinone, a derivative of anthraquinone, perylene, a derivative of perylene, carbon black are preferable in that they have high affinity with the thermoplastic resin and are difficult to bleed out, and carbon black This is particularly preferred.

The content of the coloring agent in the first resin layer is such that the visible light transmittance (Tv) can be 5% or less when laminated glass is manufactured using two sheets of clear glass conforming to JIS R3202 (1996). Han is not particularly limited. For example, when the said coloring agent is carbon black, the preferable lower limit of content of carbon black with respect to 100 mass % of said 1st resin layers is 0.01 mass %, and the preferable upper limit is 0.30 mass %. If the content of the carbon black is within this range, the visible light transmittance (Tv) of the colored laminated glass can be adjusted to 5% or less while preventing bleed-out. A more preferable lower limit of the content of the coloring agent is 0.02 mass%, a more preferable upper limit is 0.20 mass%, a still more preferable lower limit is 0.03 mass%, a still more preferable upper limit is 0.10 mass%, a particularly preferable upper limit is 0.08 mass%, and a most preferable upper limit is 0.08 mass%. It is 0.05 mass %.

It is preferable that the said 1st resin layer contains a plasticizer.

The plasticizer is not particularly limited as long as it is a plasticizer generally used for interlayers for laminated glass, and examples include organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters, phosphoric acids such as organic phosphoric acid compounds and organic phosphorous acid compounds A plasticizer etc. are mentioned.

As the organic plasticizer, for example, triethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di -2-ethylhexanoate, tetraethylene glycol-di-2-ethylbutyrate, tetraethylene glycol-di-n-heptanoate, diethylene glycol-di-2-ethylhexanoate, diethylene glycol-di- 2-ethylbutyrate, diethylene glycol-di-n-heptanoate, etc. are mentioned. Among them, the resin layer preferably contains triethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-2-ethylbutyrate, or triethylene glycol-di-n-heptanoate, It is more preferable that triethylene glycol-di-2-ethylhexanoate is included.

Although content of the said plasticizer in the said 1st resin layer is not specifically limited, A preferable lower limit with respect to 100 mass parts of said thermoplastic resin is 25 mass parts, and a preferable upper limit is 80 mass parts. When the content of the plasticizer is within this range, high penetration resistance can be exhibited. A more preferable lower limit of the content of the plasticizer is 30 parts by mass, and a more preferable upper limit is 70 parts by mass.

It is preferable that the said 1st resin layer contains an adhesive force modifier, when it contacts glass directly as an outermost layer.

As the adhesion modifier, for example, an alkali metal salt or an alkaline earth metal salt is preferably used. As said adhesive force regulator, salts, such as potassium, sodium, and magnesium, are mentioned, for example. Among them, magnesium salts are preferable from the viewpoint of being able to easily adjust the adhesive force between the glass and the interlayer film when manufacturing laminated glass.

As an acid which comprises the said salt, organic acids of carboxylic acids, such as octylic acid, hexylic acid, 2-ethyl butyric acid, butyric acid, acetic acid, and formic acid, or inorganic acids, such as hydrochloric acid and nitric acid, are mentioned, for example.

If necessary, the first resin layer may contain additives such as antioxidant, light stabilizer, modified silicone oil as an adhesion modifier, flame retardant, antistatic agent, moisture resistance agent, heat reflector, fluorescent agent, and heat absorber.

The said 2nd resin layer contains a thermoplastic resin. As a thermoplastic resin contained in the said 2nd resin layer, the same thermoplastic resin as contained in the said 1st resin layer is mentioned.

In addition, the second resin layer includes the plasticizer, the adhesive force modifier, and, if necessary, the antioxidant, the light stabilizer, the modified silicone oil as the adhesive force modifier, the flame retardant, the antistatic agent, the moisture resistance agent, the heat reflector, the fluorescent agent, the heat ray absorber, etc. may contain additives.

The said 2nd resin layer does not contain a coloring agent. However, a colorant may be contained as long as it is in a small amount within a range in which bleed-out or transfer does not occur. In addition, even when a part of the colorant contained in the first resin layer initially transfers to the second resin layer that does not contain the colorant, if it is a small amount within a range in which bleed-out or transfer does not occur, the second number The paper layer may contain a colorant. Specifically, for example, if the colorant is 0.001 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, no bleed-out or transfer occurs, and the excellent effects of the present invention are not impaired.

When the second resin layer contains a colorant, the same colorant as that contained in the first resin layer can be used.

In the interlayer film for colored laminated glass of the present invention, the ratio (E ₁ /E ₂ ) of the elastic modulus (E ₁ ) of the first resin layer to the elastic modulus (E ₂ ) of the second resin layer is 1.25 or more. By laminating the second resin layer having a high elastic modulus in this way, transfer to the interface of the concave portion at the time of embossing can be prevented, and variation in visible light transmittance can be prevented. It is preferable that it is 1.30 or more, and, as for the said ratio ( _E1 / _E2 ), it is more preferable that it is 1.35 or more.

In addition, the elasticity modulus of each said resin layer is measured by the following method.

After sufficiently kneading (mixing) the composition for forming the first resin layer with a mixing roll, press molding is performed at 150°C to obtain a molded body (first resin layer) having a thickness of 800 µm. The obtained molded body is punched out with a super dumbbell cutter: SDK-600 manufactured by Dumbbell Corporation to obtain a test piece. The obtained test piece is stored for 12 hours at 23°C and a humidity of 30%RH. After that, the test piece is subjected to a tensile test at 200 mm/min using Tensilon manufactured by A&D in a constant temperature room at 23°C. The gradient of the obtained stress-strain curve at a strain of 0 to 10% is calculated and used as Young's modulus. The obtained Young's modulus is taken as the elastic modulus of the first resin layer. A 2nd resin layer and another resin layer can also be measured by the same method.

Further, the first resin layer obtained by peeling the first resin layer and the second resin layer from the interlayer in a 23 ° C. environment was press-molded at 150 ° C. (150 ° C. for 10 minutes without pressurization) so that the thickness would be 800 μm. , 150°C for 10 minutes in a pressurized state), then punched out with a super dumbbell cutter: SDK-600 manufactured by Dumbbell Corporation to obtain a test piece.

Although the method of making the said ratio ( _E1 / _E2 ) 1.25 or more is not limited, The method of selecting the said thermoplastic resin used for each resin layer, etc. are mentioned. For example, the higher the degree of crosslinking of the thermoplastic resin and the higher the weight average molecular weight, the higher the modulus of elasticity of the resin layer. Moreover, the elasticity modulus of a resin layer can be adjusted also with the compounding quantity of the said plasticizer, and the elastic modulus of a resin layer becomes low, so that there are many compounding quantities of a plasticizer. Moreover, the elastic modulus of the resin layer can be adjusted also by the compounding quantity of the said coloring agent, and the elastic modulus of a resin layer becomes high, so that there are many compounding quantities of a coloring agent. Specifically, the value of E ₁ relative to E ₂ can be easily increased by setting the content of the colorant in the first resin layer to 0.07% by mass or more. By setting the content of the coloring agent in the first resin layer to 0.09% by mass or more, the value of E ₁ relative to E ₂ can be more easily increased. By setting the content of the coloring agent in the first resin layer to 0.12% by mass or more, the value of E ₁ relative to E ₂ can be further easily increased.

In the interlayer film for colored laminated glass of the present invention, the ratio (t ₁ /t ₂ ) of the thickness (t ₁ ) of the first resin layer to the thickness (t ₂ ) of the second resin layer is 2.0 or less. By making the thickness of the second resin layer relatively thick, transfer to the interface of the concave portion at the time of embossing can be prevented, and variation in visible light transmittance can be prevented. It is preferable that it is 1.5 or less, and, as for the said ratio ( _t1 / _t2 ), it is more preferable that it is 1.2 or less.

Specifically, it is preferable to set the average thickness of the first resin layer to 100 to 500 µm and the average thickness of the second resin layer to 100 µm or more.

When the average thickness of the first resin layer is in the range of 100 to 500 μm, the visible light transmittance when laminated glass is produced using two clear glasses conforming to JIS R3202 (1996) by blending the colorant (Tv) can be easily adjusted to 5% or less. A more preferable lower limit of the average thickness of the first resin layer is 150 μm, a more preferable upper limit is 450 μm, a still more preferable lower limit is 200 μm, a particularly preferable lower limit is 300 μm, and a still more preferable upper limit is 400 μm.

When the average thickness of the second resin layer is 100 μm or more, variation in the average thickness of the first resin layer can be suppressed. As for the average thickness of the said 2nd resin layer, it is more preferable that it is 200 micrometers or more, and it is still more preferable that it is 250 micrometers or more. The upper limit of the average thickness of the second resin layer is not particularly limited, but a practical upper limit is about 1000 μm.

In addition, the thickness of each resin layer of the interlayer for colored laminated glass is determined by cutting the interlayer vertically in the thickness direction so that the end surface of each resin layer is exposed with a sharp razor blade, and then the exposed end surface of the interlayer film. is observed with a digital microscope, and the thickness of each resin layer of the interlayer is measured by a scale bar (micro gauge) and a simple measuring function. As a digital microscope, "DSX500" by OLYMPUS, etc. can be used, for example. Also, in the simple measurement function, it is preferable to select a parallel width distance or a distance between two points. Further, the magnification at the time of observation is preferably 277 times, and the visual field range is preferably 980 μm×980 μm. Randomly observing 20 points of the interlayer for laminated glass with the digital microscope, and measuring the thickness of 5 points of each resin layer in the same field of view. An average value is obtained from the measurement results of a total of 20 × 5 points, that is, 100 points, and the average thickness of the first resin layer and the average thickness of the second resin layer are obtained.

The interlayer film for colored laminated glass of the present invention has a visible light transmittance (Tv) of 5% or less. As a result, excellent design properties, privacy protection properties, light blocking properties, and the like can be exhibited, and it can be suitably used for side glass, rear glass, roof glass of vehicles, window glass of buildings and the like. The visible light transmittance (Tv) of the interlayer film for colored laminated glass of the present invention is preferably 2% or less.

In addition, the said visible light transmittance is measured according to the following procedure. Laminated glass is manufactured using two sheets of clear glass conforming to JIS R3202 (1996), and a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech) is used for 20 arbitrary points of the obtained laminated glass, and JIS Based on R 3106 (1998), the visible light transmittance in the wavelength range of 380 to 780 nm of the obtained laminated glass was measured. The average value of 20 measured visible light transmittances and the standard deviation were obtained, and the value obtained by dividing the average value of visible light transmittance by the standard deviation (average value of visible light transmittance/standard deviation) was calculated as a CV value.

In addition, in the measurement of the visible light transmittance when laminated glass is manufactured, from the viewpoint that measurement variation is suppressed, the two pieces of clear glass conforming to JIS R3202 (1996) used have a thickness of 2.4 to 2.5 mm, Moreover, it is preferable that it is clear glass whose visible light transmittance of 90.0 to 91.0% of 1 sheet is preferable. Among them, it is more preferable to use clear glass having a thickness of 2.5 mm and a visible light transmittance of 90.5% per sheet.

The interlayer film for colored laminated glass of the present invention has a concave portion on at least one surface. This makes it possible to ensure degassing during the production of laminated glass. Among them, it is preferable that the concave portion has a groove shape (angular line shape) with a continuous bottom portion, and that adjacent concave portions on the angular line are regularly formed in parallel.

In the interlayer film for colored laminated glass of the present invention, when the ratio (E ₁ /E ₂ ) is 1.25 or more and the ratio (t ₁ /t ₂ ) is 2.0 or less, even when the interlayer film has an angular concave portion, it is visible. Variation in light transmittance can be prevented.

The method for producing the interlayer film for colored laminated glass of the present invention is not particularly limited, but a method in which the first resin layer and the second resin layer are extruded by a co-extrusion method is exemplified.

In the case of manufacturing the interlayer film for colored laminated glass of the present invention by the co-extrusion method, it is preferable to employ the feed block method. For the feed block method, please refer to Japanese Patent No. 5220607, for example. The manufacturing apparatus for an interlayer film for laminated glass used in the feed block method has a first extruder for forming an outermost layer. The first extruder is connected to one first supply hole formed in the layer arrangement guide, and one end of the outermost layer forming flow path is connected to the first supply hole in the layer arrangement guide. The flow path for forming the outermost layer is branched into first and second branch flow paths in the middle, and ends of the first and second branch flow paths are connected to outlets for forming the first and second outermost layer, respectively. there is.

By adopting the feed block method, for example, in the case of manufacturing an interlayer film for colored laminated glass in which only a portion of the first resin layer is disposed, the thickness and width of the first resin layer can be freely set, and An interlayer film for colored laminated glass having no color streaks or color loss can be produced.

A colored laminated glass in which the interlayer film for colored laminated glass of the present invention is laminated between a pair of glass plates is also one of the present inventions.

As the glass plate, a generally used transparent plate glass can be used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, molded plate glass, wire mesh glass, preloaded plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass. Moreover, the ultraviolet-shielding glass which has an ultraviolet-ray-shielding coat layer on the surface of glass can also be used. In addition, organic plastic spans such as polyethylene terephthalate, polycarbonate, and polyacrylate may be used.

As said glass plate, you may use two or more types of glass plates. For example, colored laminated glass in which the interlayer film for colored laminated glass of the present invention is laminated between a transparent float plate glass and a colored glass plate such as green glass is exemplified. Moreover, as said glass plate, you may use the glass plate from which 2 or more types of thicknesses differ.

According to the present invention, when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996), the visible light transmittance (Tv) is 5% or less, and the variation in visible light transmittance depending on the site is small, An interlayer film for colored laminated glass having excellent appearance and a colored laminated glass using the interlayer film for colored laminated glass can be provided.

Fig. 1 is a schematic view showing an example of an interlayer film for laminated glass in which concave portions in the form of grooves with continuous bottoms are arranged at regular intervals and parallel to each other on the surface.
Fig. 2 is a schematic view showing an example of an interlayer film for laminated glass in which concave portions in the form of grooves with continuous bottoms are parallel to each other at equal intervals and adjacent to each other on the surface.
Fig. 3 is image data of three-dimensional roughness measured by a three-dimensional roughness meter for the surface of an interlayer film for laminated glass in which recesses in the form of grooves with continuous bottoms are regularly parallel to the surface.

The embodiments of the present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples.

(Example 1)

(1) Preparation of the resin composition for the first resin layer

Polyvinyl alcohol having an average degree of polymerization of 1700 was acetalized with n-butylaldehyde to obtain polyvinyl butyral having an acetyl group content of 1 mol%, a butyral group content of 69 mol%, and a hydroxyl group content of 30 mol% (hereinafter also referred to as “PVB”). do). To 100 parts by mass of the obtained PVB, 40 parts by mass of triethylene glycol-di-2-ethylhexanoate (3GO) as a plasticizer and carbon black as a colorant were added and sufficiently kneaded with a mixing roll to obtain a resin composition for the first resin layer got The addition amount of the colorant was 0.095 mass% in 100 mass% of the first resin layer, and 0.038 mass% in 100 mass% of the entire interlayer film for colored laminated glass obtained.

(2) Preparation of the resin composition for the second resin layer

To 100 parts by mass of PVB, 40 parts by mass of triethylene glycol-di-2-ethylhexanoate (3GO) was added as a plasticizer and sufficiently kneaded with a mixing roll to obtain a resin composition for a second resin layer.

(3) Manufacture of interlayer film for colored laminated glass

By extruding the obtained 1st resin composition for resin layers and the 2nd resin composition for resin layers on conditions of an extrusion temperature of 200 degreeC using a co-extruder, the laminated body of the 2nd layer structure of the 1st resin layer/2nd resin layer is obtained. got it

(4) formation of recesses

A pair of embossing rolls formed with a large number of fine concave portions and a large number of fine convex portions are used as a fine concavo-convex transfer device, and the obtained laminate is passed through the emboss roll to form a large number of fine concave portions and a large number of fine convex portions. The formed laminate was obtained.

Furthermore, a pair of embossing rolls are used as a concavo-convex shape transfer device, and the resultant multilayer body formed with a large number of fine concave portions and a large number of fine convex portions is passed through the embossing roll, and grooves with continuous bottoms are formed on both sides of the multilayer body. An interlayer film for colored laminated glass was obtained by applying concave portions having a surface roughness (Rz) of 31 μm in which concave portions having a shape (angular line shape) were formed in parallel and at equal intervals. The pair of embossing rolls is composed of a metal roll subjected to milling on the surface using a triangular oblique mill, and a rubber roll having a JIS hardness of 45 to 75.

In addition, the said surface roughness (Rz) was measured by the method based on JIS B-0601 (1994). As the transfer conditions for forming the concave portion in the shape of a groove (angular line), the temperature of the layered product was 95°C, the roll temperature was 130°C, and the press pressure was 500 kPa.

Regarding the obtained interlayer film for colored laminated glass, the elastic modulus and thickness of each resin layer were measured by the method described above.

As a result, the elastic modulus (E ₁ ) of the first resin layer was 9.6 N/mm 2 and the thickness (t ₁ ) was 305 μm. Moreover, the elasticity modulus ( _E2 ) of the 2nd resin layer was 7.0 N/mm<2>, and the thickness ( _t2 ) was 455 micrometers.

(5) Manufacture of colored laminated glass

The obtained interlayer film for colored laminated glass was laminated between a pair of clear glasses (thickness: 1.0 mm), 5 cm long x 5 cm wide, to obtain a laminate. The obtained layered product was vacuum pressed and pressure-bonded while holding at 90°C for 30 minutes in a vacuum laminator. After crimping, crimping was performed for 20 minutes using an autoclave under conditions of 140°C and 14 MPa to obtain colored laminated glass.

(Examples 2 and 3)

An interlayer film for colored laminated glass having a three-layer structure of the second resin layer/first resin layer/second resin layer was prepared so that the amount of the colorant and the thickness of each resin layer became the values shown in Table 1, and the colored laminated glass was got it The same operation as in Example 1 was performed for the production of an interlayer film for colored laminated glass and laminated glass.

(Comparative Example 1)

In preparation of the resin composition for the first resin layer, the addition amount of the colorant is 0.052 mass% in 100 mass% of the obtained first resin layer, and 0.037 mass% in the entire 100 mass% of the obtained interlayer film for colored laminated glass. It was changed to an amount that becomes . Using this resin composition for the first resin layer, in the same manner as in Example 2, an interlayer film for colored laminated glass having a three-layer structure having a thickness of each resin layer having a value shown in Table 1 was produced, and colored laminated glass was obtained. got it

(Comparative Example 2)

In preparation of the resin composition for the first resin layer, the addition amount of the colorant is 0.043 mass% in 100 mass% of the obtained first resin layer, and 0.037 mass% in the entire 100 mass% of the obtained interlayer film for colored laminated glass. It was changed to an amount that becomes . Using this resin composition for the first resin layer, in the same manner as in Example 2, an interlayer film for colored laminated glass having a three-layer structure having a thickness of each resin layer having the values shown in Table 1 was produced.

(Examples 4 to 8, Comparative Examples 3 to 6)

An interlayer film for colored laminated glass and colored laminated glass were obtained in the same manner as in Example 1 except that the amount of the plasticizer, the concentration of the colorant, and the thickness of each resin layer were changed to the values shown in Table 2.

(evaluation)

The interlayer films for laminated glass obtained in Examples and Comparative Examples were evaluated by the following method. The results are shown in Table 1 and Table 2.

(Measurement of visible light transmittance)

For 20 arbitrary points of the obtained laminated glass, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech Co., Ltd.), based on JIS R 3106 (1998), the visible light transmittance at a wavelength of 380 to 780 nm was measured. measured.

An average value of 20 measured visible light transmittances and a standard deviation were obtained. The obtained standard deviation was divided by the average value of visible light transmittance, and a value multiplied by 100 (standard deviation/average value of visible light transmittance x 100) was calculated as a CV value.

In addition, as a result of measuring the visible light transmittance of the clear glass used in Examples and Comparative Examples, it was 90.5%.

According to the present invention, when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996), the visible light transmittance (Tv) is 5% or less, and the variation in visible light transmittance depending on the site is small, An interlayer film for colored laminated glass having excellent appearance and a colored laminated glass using the interlayer film for colored laminated glass can be provided.

Claims (4)

An interlayer film for colored laminated glass having a concave portion on at least one surface and having a visible light transmittance (Tv) of 5% or less when laminated glass is manufactured using two pieces of clear glass conforming to JIS R3202 (1996),
It consists of a laminate of at least two layers of a first resin layer containing a thermoplastic resin and a colorant, and a second resin layer containing a thermoplastic resin and no colorant,
The ratio (E 1 /E ₂ ) of the _elastic modulus (E 1 ) of the first resin layer to the elastic modulus ( _{E 2} ) of the second resin layer is 1.25 or more, and the thickness (t _{1 )} of the first resin layer is ), and the ratio (t ₁ /t ₂ ) of the thickness (t ₂ ) of the second resin layer is 2.0 or less,
The interlayer film for colored laminated glass, characterized in that the concave portion has a groove shape with a continuous bottom portion.
(However, the elastic modulus of the first resin layer and the elastic modulus of the second resin layer are values measured by the following measuring methods, respectively.
Measuring method: A molded object having a thickness of 800 μm is punched out to obtain a test piece. The obtained test piece is stored for 12 hours at 23°C and a humidity of 30%RH. After that, the test piece is subjected to a tensile test at 200 mm/min in a constant temperature room at 23°C. The gradient of the obtained stress-strain curve at a strain of 0 to 10% is calculated and used as Young's modulus. Let the obtained Young's modulus be the modulus of elasticity of the resin layer.) According to claim 1,
An interlayer film for colored laminated glass characterized in that the first resin layer is composed of a laminate of three or more layers sandwiched by two second resin layers. According to claim 1,
An interlayer film for colored laminated glass, characterized in that the concave portion has a groove shape with a continuous bottom and is regularly arranged in parallel. A colored laminated glass characterized in that the interlayer film for colored laminated glass according to any one of claims 1 to 3 is laminated between a pair of glass plates.

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